Stabilizing unsaturated amines



United States Patent '0 STABILIZING UNSATURATED AMINES Howard W. Bostand Richard C. Doss, Bartlesville, Okla.,

assiguors to Phillips Petroleum Company, a corporation of Delaware NoDrawing. Filed Dec. 23, 1957, Ser. No. 704,264

12 Claims. (Cl. 260583) This invention relates to the stabilization ofcertain unsaturated amines. In one aspect, the invention relates to amethod for treating such amines with a class of stabilizing agents.

Amines containing the fundamental structure have valuable uses as endproducts and as intermediates, but it has now been found that theseamines are unstable in the presence of even very minute amounts ofwater.

It has been found that such amines, upon long storage or storage at hightemperatures decompose in the presence of even minute quantities ofmoisture to form gaseous products and heavy, gummy products. Thus, acostly loss of the valuable amines results; further, storage of suchamines in closed vessels is hazardous and requires high pressure storagecontainers. The precise reason that very small amounts of water caneffect such a substantial decomposition of the amines is not known.

It is an object of this invention to stabilize certain unsaturatedamines against decompositioncaused by the presence of moisture. It isanother object of the invention to provide an improved method forstorage of certain unsaturated amines.

Other objects, as well as-aspects and advantages, of the invention, willbecome apparent from the study of the accompanying disclosure.

According to the invention, there is provideda process for thestabilization of unsaturated amines containing only hydrogen, carbon,and nitrogen and having the fundamental structure where R is ahydrocarbon radical, said amine containing from 4 to 30 carbon atoms,which comprises contacting said amine with a treating agent selectedfrom the group consisting of the alkali metals, the alkali metal oxides,the alkali metal acetylides, the alkali metal amides, the alkaline earthmetal acetylides, thev alkali metal alkoxides, the alkaline earth metalalkoxides, alkoxides of metals of group Ill-B of the periodic table, andGrignard reagents. of the formula RMgX wherein R is an alkyl or arylradical and X is halogen, said agent preferably containing no more thancarbon atoms per molecule.

Ordinary drying agents that absorb or adsorb water, such as magnesiumsulfate, are not effective to stabilize the amines.

Of the treating agents herein'before mentioned the alkali metals and thecompounds of alkali metals hereiubefore referredto are especiallyuseful.

r i N Ice 2 2,964,563 Patented Dec. 13,.195Q

2 The invention is particularly applicable to amines having the formulawherein R is selected from the group consisting of hydrogen and alkylradicals, each R is selected from the group consisting of hydrogen,alkyl, alkenyl, and cycloalkyl radicals, and when one R is a hydrogenradical the other R is one of the other members of the last named group,where Y is selected from the group consisting of H Ra R3 to Rr- (1\N-R4- (0) N-R and (a) v a I H Rs wherein each R is selected from thegroup consisting of alkyl, cycloalkyl, and alkenyl radicals and R is analkylene radical, and compound having from 4 to 30 carbon atoms permolecule, preferably 4 to 18 carbon atoms per molecule.

The treatment of the amines is effected by intimately contacting theamine, usually in liquid phase, with one of the agents, or even with amixture of same. More treating agent than is stoichiometricallyequivalent to the amount of water present is employed, In the usualcase, from 0.1 to 5 weight percent of treating agent based on the aminewill satisfy this requirement. Frequently, in the practice of theinvention, the amine will first be dried by conventional procedures tolower the water content to some low value, say less than one percent byweight, or even lower, before contacting with one of the agentsaccording to the invention. ,The treating agent can then, if desired, beleft in the reagent amine until just before. use or even left thereinduring use, de; pending upon such use. Or the agent can be removed so asto remove the resultant compounds resulting from a the reaction withwater, and then more of the agent can be added to provide the desiredexcess.

The treated amines are stable even at elevated temperatures; Thus, thecompounds can be stored in low pressure vessels without. loss thereofand without the expense of resorting to high-pressure tanks duringstorage and shipment.

The amines treated according to the process of the invention areusefulfor neutralizing the acidity of pe-. troleum oils in ordertoinhibit corrosion of metals by such oils. Such amines can be employed,byadding to the oils from 10-0 parts per million to 5 parts per 100parts by weight of oil. The amines can also be em, ployed to scrub gasescontaining residual HCl so as to remove the acid therefrom. Also,because of the double bond and the nitrogen atoms,.many of these aminesare useful as intermediates-for: preparing valuable chemical compoundsuseful as. surfactants, bacteriacides, and pharmaceuticals, and rubberprocessing agents.

Specific examples oiqtreating agents useful according to theinventioninclllde ethyl magnesium chloride, butyl magnesium chloride,hexyl magnesium chloride, propyl magnesium mide P 1 1 34 mag e i mchloride, dium, potassium, lithium, rubidium, cesium, sodium oxide,potassium oxide lithium Oxide, monosodium acetylide, disodiumacetylide,- monopotassium acetylide, dipotassium tyli1,. a t1m a t lidelc u bide), barium acetylide (b ar iumcarbide), sodium amide, potassiumamide, sodiumethoxide, sodium propoxid'e,

potassium ethoxide, sodium isopropoxide, rubidium butoxide, calciummethoxide; calcium ethoxide, calcium propoxide, magnesium ethoxide,barium propoxide, aluminum methoxide, aluminum ethoxide, aluminum,propoxide, aluminum octoxide, and gallium ethoxide. Specific examples ofamines to which the invention is applicable include: i

N-methyl-l-propene-l-amine N-benzyl-l-propene-l-amineN,N-dirnethyl-l-propene-l-amine N-ethyl-l-propene-l-amineN-butyl-l-propene-l-amine N-(Z-butenyl)-1-propene-l-amineN-methyl-l-pentene-l-amine N-isopropyl-l-penetene-l-amineN,N-dioctyl-l-pentene-l-amine N-hexyl-l-hexene-l-amine N,N -di(2-hexenyl -1-hexene-1-amine N-methyl-l-octene-l-amineN-naphthyl-l-octene-l-amiue N-butadienyl-l-octene-l-amineN-cyclohexyl-l-octene-l-amine N,N-diphenyl-l-octene-l-amineN-methyl-l-dodecene-l-amine N-methyl-l-hexadecene-l-amineN-heptyl-l-hexadecene-l-arnine N,N-diheptyl-l-hexadecene-l-amineN-methyl-Z-cyclohexyl-l-propene-l-amineN-ethyl-3-cyclohexyl-1-butene-1-amineN,N-diisopropyl-3-cyclohexyl-l-butene-l-amineN-phenyl-4-cyclohexyl-l-heptene-l-amineN-methyl-4-cyclopropyl-l-octene-l-amine N-methyl-1,3-butadiene-1-amineN-vinyl-1,3-butadiene-1-amine N-propyl-l,S-hexadiene-l-amineN-octyl-1,5-hexadiene-l-amine N-cyclohexyl-1,6-octadiene-l-amineN-phenyl-l ,fi-octadiene-l-amineN-naphthyl-N-phenyl-1,6-octadiene-1-amineN,N-diisopropyl-Z-phenylethene-l-amineN,N-dimethyl-2-naphthylethene-1-amineN-methyl-N-ethyl-2-phenylethene-l-amineN-methyl-N-ethyl-3-naphthyl-1-propene-l-amineN-cyclopropyl-4-naphthyl-l-heptenel-amineN-cyclohexyl-4-naphthyl-l-octene-l-amine N- S-methylhexyl-2-(4-methylphenyl) ethenel-amine N-propyl-2- 2,4,6-triethylphenyl)ethene-l-amine N,N-diethyl-3-benzyl-1-propene-l-amineN-(2,4,6-trimethylphenyl) 3-benzyl-1-butenel-amineN-ethyl-3-benzyl-3-methyl-l-butene-l-amineN-allyl-3-benzyl-l-pentene-l-arnine Nmethyl-6-benzyl-l-hexene-l-amine N,N'-dibutylethene-1,Z-diamine N,N-'-dihexylethene-1,2-diamine N,N'-di(2-propenyl) ethane-1,2-diamine N,N'-di i ,3-butadienyl)ethene-1,2-dian1ine N,N-diphenylethene-l ,Z-diamineN,N'-dibenzylethene-l,Z-diamine N,N'-diisopropylethene-1 ,Z-diamineN,N'-dioctylethene-1,Z-diamine N,N'-di( l-dodecenyl ethene- 1 ,2-diamineN -methyl-l-butene-1,4-diamine N -cyclohexyl-l-pentene-1,5-diamineN,N'-dioctyl-1-hexene-1,6-diamineN,N,N,N-tetramethyl-l-heptene-1,7-diamineN,N-didodecyl-1-octene-1,8-diamineN,N,N',N'-tetramethyl-l-nonene-1,9-diamine N-methyl-l-decene-LlO-diamine N,N'-diisopropyl-1-dodecene-l,IZ-diamineN,N-dimethylethene-1,Z-diamine N,N-diethylethene-1,2-diamineN,N'-dicyclohexylethene-1,Z-diamine N,N-di 1,3-butadienyl)ethene-1,2-diamine N ,N'-diphenylethene-1,2-diamine aN,N'-dibenzylethene-l,Z-diamine NhNl-dimethyl-l-propene-1,3-diamine N ,N-diethyl-1-butene-1,4-diamineN,N-dirnethyl-3-methyl-1,4-pentadiene-l-arnineN,N-dioctyl-2,3-diethyl-1,5-hexadiene-l-amine N,N-di(2-hexenyl)-2,3-diphenyll-propene-l-amine N-methyl-3- 2,4,7-triethylnaphthyl-l-propene-1-amine N,N-dimethyl-Z-phenylethene-l-amineN,N-diethyl-2-phenylethene-l-amineN,N-dimethyl-2-cyclohexyl-l-propene-l-amineN,N-diisopropyl-1,3-butadiene-l-amineN,N,N,N-tetraallylethene-1,2-diamineN.,N,N',N'-tetrabutylethene-1,2-diamineN,N,N',N'-tetramethylethene-1,2-diarnineN,N,N,N'-tetraoctylethene-1,2-diamine N,N-dimethyl-1-butene-1,4-diamineN ,N -dimethyl-l-butene-1,4-diamineN,N,N',N'-tetramethyl-l-butene-1,4-diarnineN,N,N',N'-tetraisopropyl-1-butene-1,4-diamineN,N-diphenyl-1-butene-1,4-diamine N,N'-divinyl-1-butene-l,4-diamineN,N,N',N-tetramethyl-l-propene-1,3-diamineN,N,N',N'-tetramethyl-l-butene-l ,3-diamineN,N'-diethyl-3-phenyl-1-propene-1,3-diamineN,N,N',N'-tetramethyl-Z-methyl-l-butene-1,3-diamine In the foregoingnames, the numbered superscripts indicate the number of the carbon atomto which the nitrogen is attached.

The invention is especially useful when applied to theN,N,N,N'-tetraalky1alkene-1,3-diarnines.

EXAMPLE I For the trials described below, 40 ml. samples of N,N,N',N'-tetramethyl-l-butene-1,3-diamine were used. This diamine wasprepared as described in Doss et al. Patent 2,800,509 and had beenpreviously dried with magnesium sulfate which was then removed from theproduct. The refractive index n 9", of the product was 1.4677.

A sample of this product which had been stored in a closed container forseveral days was sealed in a stainless steel bomb (about ml. capacity)having an attached pressure gauge. The bomb was placed in an oil bathand heated rapidly (within about 20 minutes) to 500 F. The pressure wasrecorded as shown in Table I. The test was terminated when the pressurereached 600 p.s.i. in order to avoid exceeding the capacity of thegauge. The refractive index of the recovered product was measured.

A comparable test was made using the same diamine stabilized with onegram of sodium. These results are also presented in Table I under columnA.

The data presented in Table I clearly demonstrate improved stability ofthe diamine due to the presence of sodium. The pressure remained below45 p.s.i.g. while heating the stabilized sample to 500 F. With theunstabilized material, the pressure reached 600 p.s.i.g. when thetemperature reached 480 F. The refractive index of the products from thetwo tests shows that the sodiumstabilized product exhibited relativelylittle change.

Table I STABILIZATION 0F N,N,N'.N-TETRAMETHYL-1-BUTENE- 1,3-DIAMINE WITHSODIUM Stabilizing Agent Sodium none Refractive Index, rm": a) Beforebomb test 1. 4677 1. 4677 (b) After bomb test 1. 4741 1. 5222 1 Thepressure increased slowly to 60 p.s.l. during subsequent 60 minutes ofaging while maintaining the temperature between 450 and 500 F.

EXAMPLE II Time, minutes: Pressure, p.s.i.g.

At the end of the 60-minute period, the bomb was removed from the oilbath and cooled in a Dry Ice bath to a temperature below 0 C. The bombwas then vented and warmed to room temperature (about C.). Considerabledecomposition of the diaminewas evident: volatile gases, possiblydimethyl amine, were evolved; a gummy residue amounting to about percentby weight of the original diamine was in the bomb; and the liquid in thebomb amounted to only 19 ml. as compared with the original charge of 40ml. This testwhen' compared with Example I clearly demonstrates that thesodium must be present during the aging period in order to achievemaximum stabilization.

EXAMPLE HI Time, minutes Tempera- Pressure,

ture, F. p.s.i.g.

0. 486 0 5 468 200 10 468 230 l s 470 230 30 495 230 7 i 495 230 whereinR is selected from the group consisting of hydrogen and alkyl radicals,each R is selected from the group consisting of hydrogen, alkyl,alkenyl, and cycloalkyl radicals, and when one R is a hydrogen radicalthe other R is one of the other members of the last named group, where Yis selected from the group consisting of wherein each R is selected fromthe group consisting of alkyl, cycloalkyl and alkenyl radicals and R isan alkylene radical, said compound having from 4 to 30 carbon atoms permolecule, which comprises contacting said amine with a treating agentselected from the group consisting of the alkali metals, the alkalimetal oxides, the alkali metal acetylides, the alkali metal amides, thealkaline earth metal acetylides, the alkali metal alkoxides, thealkaline earth metal alkoxides, alkoxides of metals of group III-B ofthe periodic table, Grignard reagents of the formula R MgX where R is analkyl radical and X is a halogen, and Grignard reagents of the formula RMgX where R is an aryl radical and X is a halogen, said Grignardreagents containing a maximum of 10 carbon atoms per molecule, saidamine also containing Water, and said treating agent being employed inexcess of an amount which is stoichiometrically equivalent to the amountof water present in said amine.

. 2. A process of claim 1 wherein said amine is N,N,N,N-tetramethyl-l-butene-l,3-diamine.

3. A process of claim 1 wherein said amine is N,N,N,N'-tetramethylpropene-1,3-diamine.

4. A process of claim 1 wherein said amine is'N,N'-dimethylpropene-1,3-diamine.

5. A process of claim 1 wherein said amine is N,N,N',N-tetraethylpropene-1,3-diamine.

6. A process ofclaim 1 wherein said amine is N,N,N',N'-tetramethyl(Z-methyl-l-butene)-l,3-diamine.

7. A process for the stabilization of an unsaturated amine consisting ofhydrogen, carbon, and nitrogen wherein said amine has the formula R2YOR1=CHN/ wherein R is selected from the group consisting of hydrogenand alkyl radicals, each R is selected from the group consisting ofhydrogen, alkyl, alkenyl, and cycloalkyl radicals, and when one R is ahydrogen radical the other R is one of the other members of the lastnamed group, where Y is selected from the group consisting of H Rawherein each R is selected from the group consisting of alkyl,cycloalkyl and alkenyl radicals and R is an alkylene radical, saidcompound having from 4 to 30 carbon atoms per molecule, which comprisescontacting said amine with a treating agent consisting of calciumcarbide, said amine also containing water, and said treating agent beingemployed in excess of an amount which is stoichiometrically equivalentto the amount of water present in said amine.

8. A process for the stabilization of an unsaturated amine consisting ofhydrogen, carbon, and nitrogen wherein said amine has the formula R2YCRr=OHN wherein R is selected from the group consisting of hydrogen andalkyl radicals, each R is selected from the group consisting ofhydrogen, alkyl, alkenyl, and cyclo alkyl radicals, and when one R is ahydrogen radical the other R is one of the other members'of the lastnamed group, where Y'is selected from the group consisting of i whereineach R is selected from the group consisting of alkyl, cycloalkyl andalkenyl radicals and R is an alkylene radical, said compound having from4 to 30 carbon atoms per molecule, which comprises contacting said aminewith a treating agent consisting of an alkali metal, said amine alsocontaining water, and said treating agent being employed in excess of anamount which is stoichiometrically equivalent to the amount of waterpresent in said amine.

9. A process of claim 8 wherein said amine is N,N,N",N'-tetramethyl-l-butene-l,3-diamine.

10. A process for the stabilization of an unsaturated amine consistingof hydrogen, carbon, and nitrogen wherein said amine has the formula /R2YCRr=CHN R2 wherein R is selected from the group consisting of hydrogenand alkyl radicals, each R is selected from the group consisting ofhydrogen, alkyl, alkenyl, and cyclo alkyl radicals, and when one R is ahydrogen radical the other R is one of the other members of the lastnamed group, where Y is selected from the group consisting ofN-Rtwherein each R is selected from the group consisting of alkyl,cycloalkyl and alkenyl radicals and R is an alkylene radical, saidcompound having from 4 to 30 carbon atoms per molecule, which comprisescontacting said amine with a treating agent consisting of potassium,said amine also containing water, and said treating agent being employedin excess of an amount which is stoichiometrically equivalent tothefjamount of water present in said amine. a I

11. A process for the stabilization of an unsaturated amine consisting,of hydrogen, carbon, and nitrogen wherein said amine has the formulawherein R is selected from the group consisting of hydrogen and alkylradicals, each R is selected from the group consisting of hydrogen,alkyl, alkenyl, and cycle alkyl radicals, and when one R is a hydrogenradical the other R is one of the other members of the last named group,where Y is selected from the group consisting of References Cited in thefile of this patent UNITED STATES PATENTS 2,172,822 Tamele et al Sept.12, 1939

1. A PROCESS FOR THE STABILIZATION OF AN UNSATURATED AMINE CONSITING OFHYDROGEN, CARBON, AND NITROGEN WHEREIN SAID AMINE HAS THE FORMULA